Antimicrobial polymer coating composition and antimicrobial polymer film

Abstract

The present invention relates to an antimicrobial polymer coating composition including: a (meth)acrylate-based monomer or oligomer containing an alkylene oxide having 1 to 10 carbon atoms; a photosensitizer; and a photoinitiator, and an antimicrobial polymer film including a substrate layer including a polymer resin containing a (meth)acrylate-based repeating unit having an introduced alkylene oxide functional group having 1 to 10 carbon atoms, and a photosensitizer dispersed in the substrate layer, wherein the antimicrobial polymer film has surface energy of 32 mN/m or more.

Claims

1. A composition for an antimicrobial polymer coating, comprising a (meth)acrylate-based monomer or oligomer represented by Chemical Formula 1, containing an alkylene oxide functional group and a (meth)acrylate-based functional group; a photosensitizer; and a photoinitiator, wherein the photosensitizer includes one or more selected from the group of a porphine compound, a porphyrin compound, a chlorin compound, a bacteriochlorin compound, a phthalocyanine compound, a naphthalocyanine compound, and a 5-aminolevuline ester, and wherein a molar ratio of the alkylene oxide functional group to the (meth)acrylate-based functional group is 0.5 or more and less than 18, per 1 mol of the (meth)acrylate-based monomer or oligomer: ##STR00009## wherein, in the Chemical Formula 1, R.sub.11 and R.sub.16 are each independently hydrogen or an alkyl having 1 to 3 carbon atoms; R.sub.12 to R.sub.15 are the same as or different from each other, and are each independently an alkylene having 1 to 4 carbon atoms; and n1 to n4 are the same as or different from each other, are each independently an integer of 0 to 13, and n1+n2+n3+n4 is 1 to 13, in which random or block phases are formed by a mixed composition of one or more of the alkylene oxide functional groups.

2. The composition of claim 1, wherein the (meth)acrylate-based monomer or oligomer has a weight average molecular weight of 500 g/mol to 10,000 g/mol.

3. The composition of claim 1, wherein the photosensitizer is present 0.01 to 5 parts by weight based 100 parts by weight of the (meth)acrylate-based monomer or oligomer.

4. The antimicrobial polymer coating composition of claim 1, wherein the photosensitizer includes a porphine compound or a porphyrin compound, to which 1 to 8 of phenyl groups comprising an alkoxy group having 1 to 10 carbon atoms are introduced.

5. The composition of claim 1, further comprising an organic solvent or a surfactant.

6. The composition of claim 1, further comprising a monomer or an oligomer containing a (meth)acrylate which is different from the (meth)acrylate-based monomer or oligomer, or a monomer or an oligomer containing a vinyl group.

7. An antimicrobial polymer film comprising a cured product of the composition of claim 1.

8. The antimicrobial polymer film of claim 7, wherein the antimicrobial polymer film has a surface energy of 32 mN/m or more.

9. The antimicrobial polymer film of claim 7, wherein the antimicrobial polymer film has an oxygen permeability of 5 to 100 cc/m.sup.2 per day.

10. The antimicrobial polymer film of claim 7, wherein the antimicrobial polymer film has a thickness of 10 μm to 10,000 μm.

11. The antimicrobial polymer film of claim 7, wherein a lifetime of singlet oxygen measured using a time-resolved phosphorescent laser spectroscopy system is 350 μs or more.

12. The antimicrobial polymer film of claim 7, wherein antimicrobial activity measured according to JIS R 1702 (KS L ISO 27447; 2011) is 90% or more.

13. An electronic product comprising the antimicrobial polymer of claim 7.

14. The electronic product of claim 13, wherein the electronic product is a humidifier, a refrigerator, an air washer, or an aquarium.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the result of NMR analysis of the product of Preparation Example 1.

(2) FIG. 2 shows the result of NMR analysis of the product of Preparation Example 2.

(3) FIG. 3 shows the result of NMR analysis of the product of Preparation Example 3.

(4) FIG. 4 shows the result of NMR analysis of the product of Preparation Example 4.

(5) FIG. 5 schematically shows the method for measuring the production amount and lifetime of singlet oxygen in Experimental Example 3.

(6) FIG. 6 schematically shows a method for measuring the antimicrobial activity of the polymer films of examples and comparative examples according to JIS R 1702 (KS ISO 27447) in Experimental Example 4.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(7) Embodiments of the present invention are described in more detail by way of the examples provided below.

(8) However, the following examples are given for illustrative purposes only, and the scope of the present invention is not intended to be limited to or by these examples.

PREPARATION EXAMPLE

Preparation of (meth)acrylate-Based Oligomer Containing an Alkylene Oxide Having 1 to 10 Carbon Atoms

Preparation Example 1

(9) A (meth)acrylate-based oligomer containing an alkylene oxide having 1 to 10 carbon atoms was prepared according to the following Reaction Scheme 1.

(10) Specifically, 5 g of triethylene glycol was dispersed in a mixed solution of 5 g of potassium carbonate (K.sub.2CO.sub.3) and 50 g of dimethyl sulfoxide, and then mixed for 30 minutes (0° C., N.sub.2-purged conditions).

(11) Then, 10 g of 2-chloroethyl acrylate (M. W. of 134.56 g/mol) was added thereto and reacted for 3 hours.

(12) The reaction product was obtained through a column, and from the results of NMR analysis (FIG. 1) and GC-MS analysis (weight average molecular weight: 302.32 g/mol), it was confirmed whether an alkylene oxide (meth)acrylate of the following Reaction Scheme 1 was produced.

(13) ##STR00002##

Preparation Example 2

(14) A (meth)acrylate-based oligomer containing an alkylene oxide having 1 to 10 carbon atoms was prepared according to the following Reaction Scheme 2.

(15) Specifically, the reaction was carried out in the same manner as in Preparation Example 1, except that 7 g of PEG200 (polyethylene glycol 200) was used instead of 5 g of triethylene glycol in Preparation Example 1.

(16) The reaction product was obtained through a column, and from the results of NMR analysis (FIG. 2) and GC-MS analysis (weight average molecular weight: 390.43 g/mol), it was confirmed whether an alkylene oxide (meth)acrylate of the following Reaction Scheme 2 was produced.

(17) ##STR00003##

Preparation Example 3

(18) A (meth)acrylate-based oligomer containing an alkylene oxide having 1 to 10 carbon atoms was prepared according to the following Reaction Scheme 3.

(19) Specifically, the reaction was carried out in the same manner as in Preparation Example 1, except that 14 g of PEG400 (polyethylene glycol 400) was used instead of 5 g of triethylene glycol in Preparation Example 1.

(20) The reaction product was obtained through a column, and from the results of NMR analysis (FIG. 3) and GC-MS analysis (weight average molecular weight: 610.69 g/mol), it was confirmed whether an alkylene oxide (meth)acrylate of the following Reaction Scheme 3 was produced.

(21) ##STR00004##

Preparation Example 4

(22) A (meth)acrylate-based oligomer containing an alkylene oxide having 1 to 10 carbon atoms was prepared according to the following Reaction Scheme 4.

(23) Specifically, the reaction was carried out in the same manner as in Preparation Example 1, except that 20 g of PEG600 (polyethylene glycol 600) was used instead of 5 g of triethylene glycol in Preparation Example 1.

(24) The reaction product was obtained through a column, and from the results of NMR analysis (FIG. 4) and GC-MS analysis (weight average molecular weight: 786.91 g/mol), it was confirmed whether an alkylene oxide (meth)acrylate of the following Reaction Scheme 4 was produced.

(25) ##STR00005##

EXAMPLE

Preparation of Antimicrobial Polymer Coating Composition and Antimicrobial Polymer Film

Example 1

(26) Ethylene glycol dimethacrylate (EGDMA, Miramer M221, CAS No. 97-90-5), which is one type of alkylene oxide (meth)acrylate-based oligomer and has the following structure, was prepared.

(27) 100 g of the ethylene glycol dimethacrylate, 5 g of trimethylolpropane triacrylate (TMPTA), 1 g of photosensitizer 5,10,15,20-tetrakis(4-methoxyphenyl)-porphine (CAS No. 22112-78-3), 2 parts by weight of a photoinitiator (trade name: Darocure TPO), 0.1 g of a surfactant (trade name: RS90 DIC), 50 g of toluene, and 50 g of ethanol were mixed to prepare an antimicrobial polymer coating solution (solid content concentration of 50%).

(28) Then, the antimicrobial polymer coating solution was coated using a #10 bar, and then cured at a rate of 2 m/min using a UV lamp of 0.2 J/cm.sup.2 to prepare an antimicrobial polymer film having a thickness of 10 μm.

(29) ##STR00006##

Examples 2 to 5

(30) The respective antimicrobial polymer coating solutions (solid content concentration of 50%) and the respective antimicrobial polymer films (thickness of 10 μm) were prepared in the same manner as in Example 1, except that the respective alkylene oxide(meth)acrylate-based oligomers of Preparation Examples 1 to 4 were used instead of ethylene glycol dimethacrylate of Example 1.

COMPARATIVE EXAMPLES

Comparative Example 1

(31) An antimicrobial polymer coating solution (solid content concentration of 50%) and an antimicrobial polymer film (thickness of 10 μm) were prepared in the same manner as in Example 1, except that methyl methacrylate (MMA) was used instead of ethylene glycol dimethacrylate of Example 1.

Comparative Example 2

(32) An antimicrobial polymer coating solution (solid content concentration of 50%) and an antimicrobial polymer film (thickness of 10 μm) were prepared in the same manner as in Example 1, except that methoxy PEG600 methacrylate (Miramer M193, MPEG600MA) was used instead of ethylene glycol dimethacrylate of Example 1, and a UV lamp of 0.1 J/cm.sup.2 was used instead of a UV lamp of 0.2 J/cm.sup.2 during coating.

(33) ##STR00007##

Comparative Example 3

(34) An antimicrobial polymer coating solution (solid content concentration of 50%) and an antimicrobial polymer film (thickness of 10 μm) were prepared in the same manner as in Example 1, except that trimethylol propane (EO).sub.9 triacrylate (TMP(EO).sub.9TA, Miramer M3190) having the following structure was used instead of ethylene glycol dimethacrylate of Example 1.

(35) ##STR00008##

EXPERIMENTAL EXAMPLE

Experimental Example 1: Water Contact Angle and Surface Energy of Polymer Films

(36) The water contact angle and surface energy of each polymer film of the examples and comparative examples were measured according to ASTM D7490-13 [Standard Test Method for Measurement of the Surface Tension of Solid Coatings, Substrates and Pigments using Contact Angle Measurements], and the results are shown in Table 1 below.

Experimental Example 2: Measurement of Oxygen Permeability of Polymer Films

(37) The oxygen permeability of each polymer films of the examples and comparative examples was measured at 25° C. under a 60 RH % atmosphere using an Oxygen Permeation Analyzer (Model 8000, Illinois Instruments product) according to ASTM D 3595.

Experimental Example 3: Measurement of the Production Amount and Lifetime of Singlet Oxygen of the Polymer Films of Examples and Comparative Examples

(38) The production amount and lifetime of singlet oxygen of each polymer film of the examples and comparative examples were measured using a time-resolved phosphorescent laser spectroscopy system shown schematically in FIG. 5.

(39) Specifically, .sup.1O.sub.2 (singlet oxygen) exhibits photoluminescence at 1275 nm. Accordingly, the presence/absence of production of .sup.1O.sub.2 and the relative amount were measured by using a near infrared photomultiplier tube (NIR-PMT) in a wavelength range of 900 nm to 1400 nm, and the movement of .sup.1O.sub.2 was observed through a time-resolved spectrum.

(40) In the case of NIR-PMT, a photoluminescence value in the wavelength region of 900 to 1400 nm could be obtained. Since singlet oxygen exhibited light emission at 1275 nm, in order to optionally detect light emission at 1275 nm, only the light emission (PL) value detected at 1275 nm was obtained by mounting an M/C (monochromator) in front of PMT.

Experimental Example 4: Measurement of Antimicrobial Activity of Polymer Films of Examples and Comparative Examples

(41) The antimicrobial activities of the polymer films of the examples and comparative examples were measured by the method shown schematically in FIG. 6 according to JIS R 1702.

(42) TABLE-US-00001 TABLE 1 Singlet oxygen (.sup.1O.sub.2) Contract Production angle [EO]/ Oxygen amount (@ Surface [Acryl] permeability (relative Lifetime water, energy Antimicrobial Molar ratio (cc/m.sup.2 .Math. day) value) (us) °) (mN/m) activity Comparative — <5 1 (reference) 20 94.2 25.8  <90% Example 1 Example 1 1 32 1.5 330~350 79.2 32.7 91.4% Example 2 2 30 1.6 330~350 77.5 34.5 94.8% Example 3 4 25 1.6 350~370 75.0 36.1 96.5% Example 4 9 22 1.7 350~370 60.8 43.2 >99.9%  Example 5 13 20 1.6 350~370 58.5 45.6 >99.9%  Comparative 26 <5 0.4 35 80.5 31.5  <90% Example 2 Comparative 18 <5 0.8 80~85 83.1 29.8  <90% Example 3 *Note: the molar ratio of [EO]/[Acryl] means a value obtained by dividing the number of moles of ethylene oxide by the number of moles of the acryl functional group, based on 1 mole of the monomer (oligomer) used as a raw material in each of Comparative Examples 1 to 3 and Examples 1 to 5.

(43) According to Table 1 above, it can be confirmed that in the case where a polymer film was produced using a (meth)acrylate-based oligomer containing an alkylene oxide having 1 to 10 carbon atoms (Examples 1 to 5), the polymer film shows a low contact angle as compared with the case of using a (meth)acrylate-based oligomer not containing any alkylene oxide having 1 to 10 carbon atoms (Comparative Example 1), the surface energy satisfies a high range of 32 mN/m or more (specifically, for example, 32 mN/m to 50 mN/m), and the antimicrobial activity is as high as 90% or more.

(44) This difference is due to the inclusion or non-inclusion of an alkylene oxide having 1 to 10 carbon atoms. In the case of including an alkylene oxide having 1 to 10 carbon atoms, it can be seen that the difference is due to the improvement in the hydrophilicity of the polymer film.

(45) Further, it can be seen that Examples 1 to 5 commonly use a (meth)acrylate-based oligomer containing an alkylene oxide having 1 to 10 carbon atoms as a raw material of the composition, and the surface energy of the prepared polymer film differs depending on the molar ratio of the alkylene oxide functional group to the (meth)acrylate-based functional group.

(46) In particular, it can be confirmed that the polymer films in which the molar ratio of the alkylene oxide functional group to the (meth)acrylate-based functional group (note: [EO]/[Acyl]) is 8 or more and 15 or less, and the surface energy is 40 mN/m or more (Examples 4 and 5), exhibit antimicrobial activity of 99.9% or more.

(47) On the other hand, when the molar ratio ([EO]/[Acyl]) of the alkylene oxide functional group to the (meth)acrylate-based functional group is 18 or more (Comparative Examples 2 and 3), the relative mole number of the (meth)acrylate-based functional group relative to the alkylene oxide functional group is small, and thus the film was not formed under the conditions of visible light of the same intensity as that of the examples, and as a result of irradiating visible light of a relatively high intensity, it could be formed into a polymer film for the first time.

(48) It can be confirmed that with such high intensity visible light, the film of Comparative Example 2 causes photobleaching, and the production amount of singlet oxygen is rather decreased and the antimicrobial property is decreased as compared with the examples.